JPH08231788A - Propylene/ethylene random copolymer resin composition - Google Patents

Abstract

PURPOSE: To obtain a resin composition having excellent heat resistance, rigidity and transparency and useful as a food vessel or a medical device, etc., by blending a specific olefin copolymer with a specific phosphorus compound and a complex salt compound. CONSTITUTION: The objective composition is obtained by blending (A) 100 pts.wt. of a propylene/ethylene random copolymer resin containing 0.1-6.0wt.% ethylene and having 1-100g/10min melt flow rate with (B) 0.01-1.0 pt.wt. of a compound of formula I (R1 is direct bonding, S or a 1-4C alkylidene; R2 and R3 are each H or a 1-8C alkyl; M is a 1-3 valance metal; (n) is 0-3) or of formula II (R4 is same as R2 ) and (C) 0.01-0.5 pt.wt. of a compound of the formula; [Al2 Li(OH)6 ]n X.mH2 O (X is an anion; (m) is 0-3; (n) is a valence number of X).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a propylene / ethylene random copolymer resin composition having excellent transparency, heat resistance and rigidity.

[0002]

2. Description of the Related Art Polypropylene resin has excellent heat resistance, chemical resistance, and electrical characteristics, and further has rigidity, tensile strength,
Since it has excellent transparency and processability, it has been widely used in injection molding, film molding, sheet molding, blow molding and other molding methods.

However, when the polypropylene resin composition is used in food containers, medical instruments, physics and chemistry experimental instruments, etc., heat resistance and transparency are still insufficient.

Regarding the improvement of heat resistance, JP-A-61-220
9207, JP 62-104810, JP 62-104811, and JP 62-1048.
No. 12, JP-A-62-104813, JP-A No. 1-311106, JP-A No. 1-318011, and JP-A No. 2-166104, titanium, magnesium, halogen, and Using a catalyst formed by combining a titanium-containing solid component containing an electron donor, a component in which an organoaluminum compound and an electron donor are combined, and an organosilicon compound having a Si—O—C bond and / or a mercapto group A method of imparting heat resistance to the polypropylene resin itself by polymerizing propylene to produce a highly crystalline polypropylene resin, or JP-A-62-209151 and JP-A-62-243635.
JP-A-63-37148, JP-A-63-
210152, JP-A-63-243150, JP-A-63-284242, JP-A-2-49.
No. 047, Japanese Patent Laid-Open No. 2-102242, etc.
A method of adding an organophosphate metal salt compound as a nucleating agent to a polypropylene resin is disclosed.

However, transparency cannot be achieved by these techniques alone, and heat resistance is not sufficient.

Regarding improvement of transparency, Japanese Patent Laid-Open No. 54-54
As described in JP-A-88950 and JP-A-58-215446, a method for producing a random copolymer portion by incorporating ethylene into the resin composition, a carboxylic acid metal salt, and an aromatic phosphoric acid There is a method of adding additives such as metal salts and sorbitol compounds. Among these, the addition of a sorbitol-based compound is most effective in improving transparency, but there are problems that heat resistance is insufficient and odor generation and elution are poor. Further, sorbitol-based compounds are expensive and therefore economically disadvantageous.

As described above, although some improvements have been found in terms of heat resistance and transparency, polypropylene resin compositions having these in a well-balanced manner have not yet been obtained. is there.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a propylene / ethylene random copolymer resin composition having excellent heat resistance, rigidity and transparency which can be used in food containers, medical instruments, physics and chemistry experimental instruments and the like. It is provided.

[0009]

Means for Solving the Problems As a result of diligent studies, the present inventors have found that a propylene / ethylene random copolymer is blended with an organophosphate metal salt compound and a lithium aluminum complex hydroxide salt compound. As a result, they have found that the above problems can be solved, and have completed the present invention.

That is, the propylene / ethylene random copolymer composition of the present invention has an ethylene content of 0.1 to 0.1.
6.0 wt% and melt flow rate (MF
R) is 1 to 100 g / 10 minutes, relative to 100 parts by weight of the propylene / ethylene random copolymer resin composition.
The following is represented by 0.01 to 1.0 part by weight of the organophosphate metal salt compound represented by the general formula (I) or (II) of the chemical formula 1 or 2 and the general formula (III) of the chemical formula 3. It is characterized in that it comprises 0.01 to 0.5 parts by weight of a lithium aluminum complex hydroxide salt compound.

[0011]

Embedded image (However, R ₁ is a direct bond or sulfur or a C _1-4 alkylidene group, R ₂ and R ₃ are H or a C _1-8 alkyl group, M is a monovalent metal atom, and n is 1 to 3 Is an integer.)

[0012]

Embedded image (However, R ₄ is H or a C _1-8 alkyl group, and M is 1 to
Trivalent metal atom, n is an integer of 1 to 3. )

[0013]

Embedded image (However, in the formula, X is an inorganic or organic anion, n is the valence of the anion X, and m is a number of 3 or less.)

The ethylene content in the propylene / ethylene random copolymer resin of the present invention is 0.1 to 6.0% by weight, preferably 1.0 to 4.0% by weight, and MF.
R is 1 to 100 g / 10 minutes, preferably 3 to 50 g
/ 10 minutes is required.

When the ethylene content is less than this range, the impact resistance, which is a characteristic of the propylene / ethylene random copolymer resin, decreases, and when it exceeds this range, the rigidity and heat resistance decrease.

If the MFR is less than this range, the fluidity at the time of molding is lowered and the moldability is lowered, and if it exceeds this range, the rigidity and heat resistance are lowered.

The method for producing the propylene / ethylene random copolymer resin of the present invention is not particularly limited, but it can be obtained by applying a gas phase polymerization method in which propylene and ethylene are simultaneously supplied in the presence of a stereoregular catalyst. .

Many stereoregular catalysts are known,
It may be arbitrarily selected from them, but typically, a catalyst component obtained by contacting titanium trichloride with an electron-donating compound such as ether or carboxylic acid ester, or titanium tetrachloride with carboxylic acid ester or alkoxy. A catalyst in which a catalyst component in which an electron-donating compound such as silane is supported on a magnesium compound, an organoaluminum compound such as diethylaluminum chloride and triethylaluminum, and more preferably, the above-mentioned electron-donating compound as a third component are combined. Can be mentioned.

In the present invention, 100 parts by weight of the above-mentioned propylene / ethylene random copolymer resin is added to the organic phosphate metal salt compound represented by the following general formula (I) or (II) 0.01 to 1.0 parts by weight, preferably 0.05 to 0.3 parts by weight, and the following general formula (II)
The lithium aluminum complex hydroxide salt compound represented by I) is 0.01 to 0.5 parts by weight, preferably 0.03 to
Add 0.15 parts by weight. If the organophosphate metal salt compound and the lithium aluminum complex hydroxide salt compound are less than the above ranges, the improvement in rigidity such as flexural modulus, heat distortion temperature, heat resistance and transparency, which is the object of the present invention, is not sufficient.
Further, even if it exceeds the above range, the further improvement effect is not obtained, and the cost is increased, which is not preferable.

[0020]

Embedded image (However, R ₁ is a direct bond or sulfur or a C _1-4 alkylidene group, R ₂ and R ₃ are H or a C _1-8 alkyl group, M is a monovalent metal atom, and n is 1 to 3 Is an integer.)

[0021]

Embedded image (However, R ₄ is H or a C _1-8 alkyl group, and M is 1 to
Trivalent metal atom, n is an integer of 1 to 3. )

[0022]

Embedded image (However, in the formula, X is an inorganic or organic anion, n is the valence of the anion X, and m is a number of 3 or less.)

Examples of the organophosphoric acid metal salt compound represented by the general formula (I) of the chemical formula 1 usable in the present invention include sodium-2,2'-methylene-bis- (4,6-di-t-). Butylphenyl) phosphate, sodium-2,2'-
Ethylidene-bis- (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-
Bis- (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-ethylidene-bis- (4
6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis- (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis -(4-methyl-6-t
-Butylphenyl) phosphate, lithium-2,2
′ -Methylene-bis- (4-ethyl-6-t-butylphenyl) phosphate, calcium-bis- [2,2
'-Thiobis- (4-methyl-6-t-butylphenyl) phosphate], calcium-bis- [2,2'
-Thiobis- (4-ethyl-6-t-butylphenyl)
Phosphate], calcium-bis- [2,2'-thiobis- (4,6-di-t-butylphenyl) phosphate], magnesium-bis- [2,2'-thiobis- (4,6-di] -T-butylphenyl) phosphate], magnesium-bis- [2,2'-thiobis-
(4-t-octylphenyl) phosphate], sodium-2,2'-butylidene-bis- (4,6-di-
Methylphenyl) phosphate, sodium-2,2
′ -Butylidene-bis- (4,6-di-t-butylphenyl) phosphate, sodium-2,2′-t-octylmethylene-bis- (4,6-di-methylphenyl) phosphate, sodium- 2,2'-t-octylmethylene-bis- (4,6-di-t-butylphenyl) phosphate, calcium-bis- [2,2'-
Methylene-bis- (4,6-di-t-butylphenyl)
Phosphate], magnesium-bis- [2,2'-
Methylene-bis- (4,6-di-t-butylphenyl)
Phosphate], barium-bis- [2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate], sodium-2,2'-methylene-bis- (4-methyl-) 6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis- (4-
Ethyl-6-t-butylphenyl) phosphate, sodium (4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate, calcium-bis-[(4 4'-dimethyl-6,6'-di-
t-butyl-2,2'-biphenyl) phosphate], sodium-2,2 'ethylidene-bis- (4-
s-Butyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis- (4,6
-Di-methylphenyl) phosphate, sodium-
2,2'-methylene-bis- (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis- (4,6-di-t-butylphenyl) phosphate, calcium- Bis- [2,2'-ethylidene-bis- (4,6-di-t-butylphenyl) phosphate], magnesium-bis- [2,2'-ethylidene-bis- (4,6-di-t) -Butylphenyl) phosphate], barium-bis- [2,2'-ethylidene-bis- (4,6-di-t-butylphenyl) phosphate], aluminum-tris- [2,2'-methylene- Bis- (4,6-di-t-butylphenyl) phosphate] or aluminum-tris- [2,2'-
Ethylidene-bis- (4,6-di-t-butylphenyl) phosphate] and the like. Of these,
Especially sodium-2,2'-methylene-bis- (4,6
-Di-t-butylphenyl) phosphate is preferred.

Further, as the organophosphoric acid metal salt compound represented by the general formula (II) of Chemical formula 2, sodium-bis-
(4-t-butylphenyl) phosphate, sodium-bis- (4-methylphenyl) phosphate, sodium-bis- (4-ethylphenyl) phosphate, sodium-bis- (4-i-propylphenyl)
Phosphate, sodium-bis- (4-t-octylphenyl) phosphate, potassium-bis- (4-
t-Butylphenyl) phosphate, calcium-bis- (4-t-butylphenyl) phosphate, magnesium-bis- (4-t-butylphenyl) phosphate, lithium-bis- (4-t-butylphenyl)
Examples thereof include phosphate, aluminum-bis- (4-t-butylphenyl) phosphate, and a mixture of two or more kinds thereof.

Specific examples of the lithium aluminum complex hydroxide salt compound usable in the present invention include those described in JP-A-5-179052. That is, the inorganic or organic anion represented by X in the general formula is obtained from carbonic acid, sulfuric acid, chlorine oxyacid (for example, perchloric acid), phosphorus oxyacid (phosphoric acid, phosphorous acid, metaphosphoric acid), or the like. One or a combination of two or more of the above-mentioned anions is preferable, but acetic acid, propionic acid, adipic acid, benzoic acid, phthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, p-oxybenzoic acid, salicylic acid, picrin. Anions obtained from acids and the like are mentioned.

The propylene / ethylene random copolymer resin composition of the present invention contains silica, alumina, talc, mica, clay, kaolin, wollastonite, zeolite, silica-alumina, calcium carbonate, and hydroxide depending on the application. Aluminum, titanium dioxide, zinc oxide, magnesium oxide, zirconium oxide, zinc sulfide, barium sulfate, calcium sulfate, calcium phosphate, magnesium phosphate, aluminum silicate, silicon nitride, glass, hydrotalcite, etc. Thing, or glass fiber, potassium titanate fiber,
Inorganic filler such as carbon fiber, carbon black, graphite, mica ceramics fiber, metal fiber or the like, or the inorganic filler surface-treated with a silane-, titanate-, boron-, aluminate-, zircoaluminate-based coupling agent. , Organic fillers such as wood powder, pulp, synthetic fibers, and natural fibers, phenol-based, thioether-based, phosphorus-based antioxidants, light stabilizers, clarifying agents, nucleating agents such as organic carboxylic acids or metal salts thereof For the purpose of the present invention, a lubricant, an antistatic agent, an antifogging agent, an antiblocking agent, a pigment, a heavy metal deactivator, a radical generator such as a peroxide, a dispersant such as metal soaps, or a neutralizing agent. It can be blended within a range that does not impair it.

The propylene / ethylene random copolymer resin composition of the present invention is prepared by mixing the above components using a Henschel mixer, super mixer, ribbon blender or the like,
Normal single screw extruder, twin screw extruder, Banbury mixer,
It can be obtained by melt-kneading with a Brabender, a roll or the like in a temperature range of 170 to 300 ° C.

[0028]

EXAMPLES The present invention will be described in detail with reference to the following examples and comparative examples, but the present invention is not limited thereto. Examples 1-5 1. Raw material (a) Propylene / ethylene random copolymer (1) Ethylene content: 2.6% by weight, MFR: 15 g / 10 minutes (measured at 230 ° C. and 2.16 kg; the same applies hereinafter) (RPP-
1) (2) Ethylene content: 3.5% by weight, MFR: 9 g / 10 min (RPP-2) (b) Organic phosphoric acid metal salt compound Sodium-2,2'-methylene-bis- (4,6 -Di-t-butylphenyl) phosphate (manufactured by Asahi Denka Co., Ltd., trade name NA-11) (c) Lithium aluminum complex hydroxide salt compound represented by general formula (III) Mizusawa Chemical Industry Co., Ltd. ), Trade name MIZUKARAC (d) Other additives Phenol type antioxidant Phosphorus type antioxidant Neutralizer 2. Kneading method With respect to 100 parts by weight of the propylene / ethylene random copolymer (a), the compounding amounts of the organic phosphate metal salt compound (b) and the lithium aluminum complex hydroxide salt compound (c) shown in Table 1 below, Each of 0.05 parts by weight of a phenol-based antioxidant, a phosphorus-based antioxidant and a neutralizing agent (d) were mixed in a Henschel mixer and then melt-kneaded using a 50 mmφ single-screw extruder. The die was extruded at a die outlet temperature of 230 ° C. to obtain pellets. 3. Molding method The obtained pellets were heated at a resin temperature of 210 by an injection molding machine.
° C., injection pressure 400 kg / cm ² and at a mold temperature of 30 ° C., to prepare a test piece. 4. Physical property measurement Physical property measurement of each test piece was performed by the following methods. The measurement results are shown in Table 1 below. (1) MFR: Measured according to JIS K7210. (2) Haze value (%): Using a 1 mm thick test piece, AS
It measured based on TM D1003-61. (3) Flexural modulus (kgf / cm ² ): JIS K72
It measured based on 03. (4) Heat distortion temperature (° C.): Measured with a load of 4.6 kg5 / cm ² according to JIS K7207. Comparative Example 1 According to the blending amount shown in Table 1 below, only the same propylene / ethylene random copolymer (a) and the additive (d) as in Examples 1 to 4 were blended, and pellets were prepared under the same conditions as those in Examples. The physical properties were measured. The results are shown in Table 1 below. Comparative Example 2 As an additive, except that p-t-butylbenzoic acid aluminum salt (Dainippon Ink and Chemicals, Inc., trade name Shell Nucleating Agent) was added to Comparative Example 1 according to the compounding amounts shown in Table 1 below. The pellets were prepared under the same conditions as in the examples, and the physical properties were measured. The results are shown in Table 1 below. Comparative Examples 3 and 4 Pellets were prepared under the same conditions as in Examples except that NA-11 (b) was added as the additive according to the blending amount shown in Table 1 below without using Mizukarak (c) of the Examples. Then, the physical properties were measured. The results are shown in Table 1 below.

[0029]

[Table 1]

As is clear from the results shown in Table 1, the propylene / ethylene random copolymer resin composition of the present invention is a comparative composition in which the organophosphate metal salt compound and the lithium aluminum complex hydroxide salt compound are not blended. It is superior in heat resistance, rigidity and transparency as compared with the propylene / ethylene random copolymer resin composition of the example.

[0031]

[Effect] The propylene / ethylene random copolymer resin composition of the present invention is excellent in heat resistance, rigidity and transparency, and can be widely used for applications such as food containers, medical instruments and physicochemical laboratory instruments.

Claims (3)

[Claims] 1. An ethylene content of 0.1 to 6.0% by weight and a melt flow rate (MFR) of 1 to 100.
With respect to 100 parts by weight of the propylene / ethylene random copolymer resin of g / 10 minutes, 0 of the organophosphate metal salt compound represented by the following general formula (I) or (II) of chemical formula 1 or chemical formula 2 is used. 0.01 to 1.0 part by weight, and the general formula (I
A propylene / ethylene random copolymer resin composition obtained by blending 0.01 to 0.5 part by weight of the lithium aluminum composite hydroxide salt compound represented by II). Embedded image (However, R ₁ is a direct bond or sulfur or a C _1-4 alkylidene group, R ₂ and R ₃ are H or a C _1-8 alkyl group, M is a monovalent metal atom, and n is 1 to 3 Is an integer of.) (However, R ₄ is H or a C _1-8 alkyl group, and M is 1 to
Trivalent metal atom, n is an integer of 1 to 3. ) [Chemical 3] (However, in the formula, X is an inorganic or organic anion, n is the valence of the anion X, and m is a number of 3 or less.) 2. A propylene / ethylene random copolymer resin having an ethylene content of 1.0 to 4.0% by weight, a melt flow rate (MFR) of 3 to 50 g / 10 minutes, and an organophosphate metal salt. Compounding amount of 0.05-0.3
The propylene / ethylene random copolymer resin composition according to claim 1, wherein the blending amount of the lithium aluminum composite hydroxide salt compound is 0.03 to 0.15 part by weight. 3. An organic phosphoric acid metal salt compound is sodium-
The propylene / ethylene random copolymer resin composition according to claim 1 or 2, which is 2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate.